Supported catalyst for olefin polymerization and preparation method for polyolefin using the same

ABSTRACT

The present invention relates to a supported catalyst for olefin polymerization to which a novel transition metal compound and a co-catalyst compound are bound, and a preparation method for polyolefin using the supported catalyst. The transition metal compound bound to the catalyst of the present invention provides high activity for olefin-based monomers in heterogeneous reaction as well as in homogeneous system. Particularly, a polyolefin with higher molecular weight can be prepared by using the supported catalyst containing the transition metal compound bound to a support, rather than using the novel transition metal compound in a non-supported status, or the conventional transition metal compound in a supported or non-supported status.

FIELD OF THE INVENTION

The present invention relates to a supported catalyst for olefinpolymerization, and a preparation method for polyolefin using the same.

BACKGROUND OF THE INVENTION

Sustainable attempts have been made in the fields of academy andindustry to prepare a polyolefin with desired properties using a varietyof homogenous catalysts since Prof. Kaminsky developed the homogeneousZiegler-Natta catalyst using a Group 4 metallocene compound activatedwith a methylaluminoxane co-catalyst in the late 1970's.

The conventional heterogeneous catalysts in ethylene/α-olefincopolymerization not only provide a low quantity of α-olefinincorporation but cause the α-olefin incorporation to occur primarily inthe polymer chain with low molecular weight only. Contrarily, thehomogenous catalysts in ethylene/α-olefin copolymerization lead toinduce a high quantity of α-olefin incorporation and provide uniformα-olefin distribution.

In contrast to the heterogeneous catalysts, however, the homogenouscatalysts are hard of providing a polymer with high molecular weight(for example, weight average molecular weight of at least 10,000,000).

With low molecular weight, the polymers encounter a limitation indevelopment of their usage, such as being inapplicable to the productsrequired to have high strength. For that reason, the conventionalheterogeneous catalysts have been used in the industrial manufacture ofpolymers, and the usage of the homogeneous catalysts is confined to themanufacture for some grades of polymer.

DISCLOSURE OF INVENTION Technical Problem

It is therefore an object of the present invention to provide asupported catalyst for olefin polymerization that has high catalyticactivity for heterogeneous reaction as well as homogeneous reaction andprovides a polyolefin with high molecular weight.

It is another object of the present invention to provide a method forpreparing a polyolefin using the supported catalyst.

Technical Solution

To achieve the objects, the present invention is to provide a supportedcatalyst comprising a transition metal compound represented by thefollowing formula 1 and a co-catalyst compound, where the transitionmetal compound and the co-catalyst are bound to a support:

In the formula 1, M is a Group 4 transition metal;

Q¹ and Q² are independently a halogen, C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl,C₂-C₂₀ alkynyl, C₆-C₂₀ aryl, C₁-C₂₀ alkyl C₆-C₂₀ aryl, C₆-C₂₀ arylC₁-C₂₀ alkyl, C₁-C₂₀ alkylamido, C₆-C₂₀ arylamido, or C₁-C₂₀ alkylidene;

R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are independently hydrogen;C₁-C₂₀ alkyl with or without an acetal, ketal, or ether group; C₂-C₂₀alkenyl with or without an acetal, ketal, or ether group; C₁-C₂₀ alkylC₆-C₂₀ aryl with or without an acetal, ketal, or ether group; C₆-C₂₀aryl C₁-C₂₀ alkyl with or without an acetal, ketal, or ether group; orC₁-C₂₀ silyl with or without an acetal, ketal, or ether group, whereinR¹ and R² can be linked to each other to form a ring; R³ and R⁴ can belinked to each other to form a ring; and at least two of R⁵ to R¹⁰ canbe linked to each other to form a ring; and

R¹¹, R¹², and R¹³ are independently hydrogen; C₁-C₂₀ alkyl with orwithout an acetal, ketal, or ether group; C₂-C₂₀ alkenyl with or withoutan acetal, ketal, or ether group; C₁-C₂₀ alkyl C₆-C₂₀ aryl with orwithout an acetal, ketal, or ether group; C₆-C₂₀ aryl C₁-C₂₀ alkyl withor without an acetal, ketal, or ether group; C₁-C₂₀ silyl with orwithout an acetal, ketal, or ether group; C₁-C₂₀ alkoxy; or C₆-C₂₀aryloxy, where R¹¹ and R¹², or R¹² and R¹³ can be linked to each otherto form a ring.

In the transition meta compound of the formula 1, preferably, M istitanium (Ti), zirconium (Zr), or hafnium (Hf); Q¹ and Q² areindependently methyl or chlorine; R¹, R², R³, R⁴, and R⁵ areindependently hydrogen or methyl; and R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², andR¹³ are independently hydrogen.

Further, the co-catalyst compound may be at least one selected from thegroup consisting of compounds represented by the following formula 6, 7,or 8.

—[Al(R⁶¹)—O]_(a)—  [Formula 6]

In the formula 6, R⁶¹ is independently a halogen radical, a C₁-C₂₀hydrocarbyl radical, or a halogen-substituted C₁-C₂₀ hydrocarbylradical; and a is an integer of 2 or above.

D(R⁷¹)₃   [Formula 7]

In the formula 7, D is aluminum (Al) or boron (B); and R⁷¹ isindependently a halogen radical, a C₁-C₂₀ hydrocarbyl radical, or ahalogen-substituted C₁-C₂₀ hydrocarbyl radical.

[L-H]⁺[Z(A)₄]⁻ or [L]⁺[Z(A)₄]⁻  [Formula 8]

In the formula 8, L is a neutral or cationic Lewis acid; Z is a Group 13element; and A is independently a C₆-C₂₀ aryl or C₁-C₂₀ alkyl radicalhaving at least one hydrogen atom substituted with a halogen radical, aC₁-C₂₀ hydrocarbyl radical, a C₁-C₂₀ alkoxy radical, or a C₆-C₂₀ aryloxyradical.

In the co-catalyst compound, R⁶¹ in the formula 6 is methyl, ethyl,n-butyl, or isobutyl. In the formula 7, D is aluminum, and R⁷¹ is methylor isobutyl; or D is boron, and R⁷¹ is pentafluorophenyl. In the formula8, [L-H]⁺ is a dimethylanilinium cation, [Z(A)₄]⁻ is [B(C₆ ^(F) ₅)₄]⁻,and [L]⁺ is [(C₆H₅)₃C]⁺.

The content of the co-catalyst compound is given such that the molarratio of a metal in the co-catalyst compound with respect to one mole ofa transition metal in the transition metal compound of the formula 1 is1:1 to 1:100,000.

Further, the support is SiO₂, Al₂O₃, MgO, MgCl₂, CaCl₂, ZrO₂, TiO₂,B₂O₃, CaO, ZnO, BaO, ThO₂, SiO₂—Al₂O₃, SiO₂—MgO, SiO₂—TiO₂, SiO₂—V₂O₅,SiO₂—CrO₂O₃, SiO₂—TiO₂—MgO, bauxite, zeolite, starch, or cyclodextrine.

On the other hand, the present invention is to provide a method forpreparing a polyolefin that comprises polymerizing at least oneolefin-based monomer in the presence of the supported catalyst.

The olefin-based monomer may be at least one selected from the groupconsisting of C₂-C₂₀ α-olefin, C₁-C₂₀ diolefin, C₃-C₂₀ cyclo-olefin, andC₃-C₂₀ cyclo-diolefin.

The polyolefin may have a weight average molecular weight (Mw) of1,000,000 to 10,000,000.

Advantageous Effects

The novel transition metal compound supported on the catalyst of thepresent invention not only has high catalytic activity and goodcopolymerization characteristic in olefin polymerization but provides apolymer with high molecular weight, so it can be used to easily preparea polymer of different grades in commercial manufacturing process.Moreover, the catalyst compound of the present invention can exhibithigher catalytic activity than the catalyst compound not fused with aheterocyclic thiophene ligand.

Particularly, the use of a supported catalyst on which the transitionmetal compound is supported results in production of a polyolefin withhigher molecular weight, than using the novel transition metal compoundin a non-supported status or the conventional transition metal compoundin either supported or non-supported status.

DETAILED DESCRIPTION OF THE INVENTION

Hereinafter, a description will be given as to a supported catalyst forolefin polymerization and a preparation method for polyolefin using thesame according to embodiments of the present invention.

In the course of repeated studies on the catalysts for olefinpolymerization, the inventors of the present invention have found out anovel ligand in which an amido ligand is linked to an ortho-phenyleneligand to form a condensed ring, and a 5-membered cyclic pi-ligandlinked to the ortho-phenylene ligand is fused with a heterocyclicthiophene ligand. Also, they have found it out that a transition metalcompound comprising the ligand exhibits higher catalytic activity andprovides a polymer with higher molecular weight than a transition metalcompound not fused with such a heterocyclic thiophene ligand.

Particularly, the inventors have also found it out that it is possibleto prepare a polyolefin with higher molecular weight when using thetransition metal compound comprising the novel ligand in combinationwith a co-catalyst compound as supported on a support, rather than usingthe novel transition metal compound in a non-supported status, or theconventional transition metal compound in either supported ornon-supported status, thereby completing the present invention.

In accordance with one embodiment of the present invention, there isprovided a supported catalyst comprising a transition metal compoundrepresented by the following formula 1 and a co-catalyst compound whichare bound to a support:

In the formula 1, M is a Group 4 transition metal;

Q¹ and Q² are independently a halogen, C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl,C₂-C₂₀ alkynyl, C₆-C₂₀ aryl, C₁-C₂₀ alkyl C₆-C₂₀ aryl, C₆-C₂₀ arylC₁-C₂₀ alkyl, C₁-C₂₀ alkylamido, C₆-C₂₀ arylamido, or C₁-C₂₀ alkylidene;

R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are independently hydrogen;C₁-C₂₀ alkyl with or without an acetal, ketal, or ether group; C₂-C₂₀alkenyl with or without an acetal, ketal, or ether group; C₁-C₂₀ alkylC₆-C₂₀ aryl with or without an acetal, ketal, or ether group; C₆-C₂₀aryl C₁-C₂₀ alkyl with or without an acetal, ketal, or ether group; orC₁-C₂₀ silyl with or without an acetal, ketal, or ether group, whereinR¹ and R² can be linked to each other to form a ring; R³ and R⁴ can belinked to each other to form a ring; and at least two of R⁵ to R¹⁰ canbe linked to each other to form a ring; and

R¹¹, R¹², and R¹³ are independently hydrogen; C₁-C₂₀ alkyl with orwithout an acetal, ketal, or ether group; C₂-C₂₀ alkenyl with or withoutan acetal, ketal, or ether group; C₁-C₂₀ alkyl C₆-C₂₀ aryl with orwithout an acetal, ketal, or ether group; C₆-C₂₀ aryl C₁-C₂₀ alkyl withor without an acetal, ketal, or ether group; C₁-C₂₀ silyl with orwithout an acetal, ketal, or ether group; C₁-C₂₀ alkoxy; or C₆-C₂₀aryloxy, wherein R¹¹ and R¹², or R¹² and R¹³ can be linked to each otherto form a ring.

In other words, the supported catalyst for olefin polymerizationaccording to the present invention contains a composition comprising atransition metal compound of the formula 1 and a co-catalyst compoundwhich are bound to a support. Hereinafter, the individual componentscontained in the supported catalyst of the present invention will bedescribed.

First of all, the supported catalyst for olefin polymerization accordingto the present invention comprises a transition metal compoundrepresented by the formula 1. The transition metal compound of theformula 1 is supported on the surface of an under-mentioned support andactivated with an under-mentioned co-catalyst compound to providecatalytic activity for olefin polymerization reaction.

The transition metal compound of the formula 1 comprises a novel ligandin which an amido ligand is linked to an ortho-phenylene ligand to forma condensed ring, and a 5-membered cyclic pi-ligand linked to theortho-phenylene ligand is fused with a heterocyclic thiophene ligand.Accordingly, the transition metal compound exhibits higher catalyticactivity for both olefin polymerization and α-olefin copolymerizationthan the transition metal compound not fused with a heterocyclicthiophene ligand. The transition metal compound can also provide apolyolefin with a wide range of properties (particularly, high molecularweight) which are hard to attain by the use of the conventionalhomogeneous/heterogeneous catalysts.

According to the present invention, in the compound of the formula 1,R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ areindependently substituted with a substituent, including acetal, ketal,and ether groups. With such substituents, the transition metal compoundcan be more favored in being supported on the surface of a support.

In the compound of the formula 1, M is preferably titanium (Ti),zirconium (Zr), or hafnium (Hf).

Preferably, Q¹ and Q² are independently halogen or C₁-C₂₀ alkyl. Morepreferably, Q¹ and Q² are independently chlorine or methyl.

R¹, R², R³, R⁴, and R⁵ are independently hydrogen or C₁-C₂₀ alkyl,preferably hydrogen or methyl. More preferably, R¹, R², R³, R⁴, and R⁵are independently hydrogen or methyl, with the provision that at leastone of R³ and R⁴ is methyl; and R⁵ is methyl.

Preferably, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ are independentlyhydrogen.

The transition metal compound of the formula 1 preferably includes theabove-mentioned substituents with a view to controlling the electronicand steric environments around the metal.

On the other hand, the transition metal compound of the formula 1 can beobtained from a precursor compound represented by the following formula2:

In the formula 2, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹² andR¹³ are as defined in the formula 1.

In this regard, the precursor compound of the formula 2 may be preparedby a method comprising: (a) reacting a tetrahydroquinoline derivativerepresented by the following formula 3 with alkyl lithium and addingcarbon dioxide to prepare a compound represented by the followingformula 4; and (b) reacting the compound of the formula 4 with alkyllithium, adding a compound represented by the following formula 5, andthen treating with an acid:

In the formulas 3, 4, and 5, R¹, R², R³, R⁴, R⁵, R⁶, R^(7, R) ⁸, R⁹,R¹⁰, R¹¹, R¹², and R¹³ are as defined in the formula 1.

In the formulas 3, 4, and 5, R¹, R², R³, R⁴, and R⁵ are independentlyhydrogen or C₁-C₂₀ alkyl, preferably hydrogen or methyl. Morepreferably, R¹, R², R³, R⁴, and R⁵ are independently hydrogen or methyl,with the provision that at least one of R³ and R⁴ is methyl; and R⁵ ismethyl. Preferably, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ areindependently hydrogen. In this manner, the precursor compound isadvantageous in securing easy accessibility and reactivity of a startingmaterial and controlling the electronic and steric environments for thedesired transition metal compound of the formula 1.

The step (a) involves reacting a tetrahydroquinoline derivative of theformula 3 with alkyl lithium and then adding carbon dioxide to form acompound of the formula 4, which process can be achieved by the methodsdisclosed in the known documents (Tetrahedron Lett. 1985, 26, 5935;Tetrahedron 1986, 42, 2571; and J. Chem. SC. Perkin Trans. 1989, 16).

In the step (b), the compound of the formula 4 is reacted with alkyllithium to activate deprotonation and produce an ortho-lithium compound,which is then reacted with a compound of the formula 5 and treated withan acid to obtain a precursor for transition metal compound of theformula 2.

The method of producing an ortho-lithium compound by reaction betweenthe compound of the formula 4 and alkyl lithium can be understood fromthe known documents (Organometallics 2007, 27,6685; and Korean PatentRegistration No. 2008-0065868). In the present invention, theortho-lithium compound is reacted with a compound of the formula 5 andtreated with an acid to produce a precursor for transition metalcompound of the formula 2.

The compound of the formula 5 can be prepared by a variety of knownmethods. For example, the following Scheme 1 can be used to prepare theprecursor for the transition metal compound of the present inventionwith ease in a one-step process, which is economically beneficial byusing inexpensive starting materials (J. Organomet. Chem., 2005,690,4213).

On the other hand, a variety of known methods can be employed tosynthesize the transition metal compound of the formula 1 from theprecursor for transition metal compound of the formula 2 obtained by theabove-stated preparation method. According to one embodiment of thepresent invention, 2 equivalents of alkyl lithium is added to theprecursor for transition metal compound of the formula 2 to inducedeprotonation for producing a dilithium compound of cyclopentadienylanion and amide anion, and (Q¹)(Q²)MCl₂ is then added to the dilithiumcompound to eliminate 2 equivalents of LiCl, thereby preparing thetransition metal compound of the formula 1.

According to another embodiment of the present invention, the compoundof the formula 2 is reacted with M(NMe₂)₄ to eliminate 2 equivalents ofHNME₂ and produce a transition metal compound of the formula 1, whereboth Q¹ and Q² are NMe₂. The transition metal compound is then reactedwith Me₃SiCl or Me₂SiCl₂ to replace the NMe₂ ligand with a chlorineligand.

On the other hand, the supported catalyst for olefin polymerizationaccording to the present invention further comprises a co-catalystcompound. The co-catalyst compound in combination with the transitionmetal compound of the formula 1 is fixed on a support and used toactivate the transition metal compound. Thus, any kind of co-catalystcompound can be used without limitation in its construction as long asit can activate the transition metal compound without deteriorating thecatalytic activity of the supported catalyst of the present invention.

In accordance with one embodiment of the present invention, theco-catalyst compound is preferably at least one selected from the groupconsisting of compounds represented by the following formula 6, 7, or 8.

—[Al(R⁶¹)—O]_(a)—  [Formula 6]

In the formula 6, R⁶¹ is independently a halogen radical, a C₁-C₂₀hydrocarbyl radical, or a halogen-substituted C₁-C₂₀ hydrocarbylradical; and a is an integer of 2 or above.

D(R⁷¹)₃   [Formula 7]

In the formula 7, D is aluminum (Al) or boron (B); and R⁷¹ isindependently a halogen radical, a C₁-C₂₀ hydrocarbyl radical, or ahalogen-substituted C₁-C₂₀ hydrocarbyl radical.

[L-H]⁺[Z(A)₄]⁻ or [L]⁺[Z(A)₄]⁻  [Formula 8]

In the formula 8, L is a neutral or cationic Lewis acid; Z is a Group 13element; and A is independently a C₆-C₂₀ aryl or C₁-C₂₀ alkyl radicalhaving at least one hydrogen atom substituted with a halogen radical, aC₁-C₂₀ hydrocarbyl radical, a C₁-C₂₀ alkoxy radical, or a C₆-C₂₀ aryloxyradical.

In this regard, the co-catalyst compound of the formula 6 is notspecifically limited in its construction, provided that it isalkylaluminoxane, and may be preferably methylaluminoxane,ethylaluminoxane, butylaluminoxane, hexylaluminoxane, octylaluminoxane,decylaluminoxane, etc.

Further, the co-catalyst compound of the formula 7 may betrialkylaluminum (e.g., trimethylaluminum, triethylaluminum,tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum,etc.); dialkylaluminum alkoxide (e.g., dimethylaluminum methoxide,diethylaluminum methoxide, dibutylaluminum methoxide, etc.);dialkylaluminum halide (e.g., dimethylaluminum chloride, diethylaluminumchloride, dibutylaluminum chloride, etc.); alkylaluminum dialkoxide(e.g., methylaluminum dimethoxide, ethylaluminum dimethoxide,butylaluminum dimethoxide, etc.); alkylaluminum dihalide (e.g.,methylaluminum dichloride, ethylaluminum dichloride, butylaluminumdichloride, etc.); trialkyl boron (e.g., trimethyl boron, triethylboron, triisobutyl boron, tripropyl boron, tributyl boron, etc.); ortris-pentafluorophenyl boron.

Further, the co-catalyst compound of the formula 8 may betrimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium n-butyltris(pentafluorophenyl)borate, N,N-dimethylanilinium benzyltris(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenypborate,N,N-dimethylaniliniumtetrakis(4-(t-triisopropylsilyl)-2,3,5,6-tetrafluorophenyl)borate,N,N-dimethylanilinium pentafluorophenoxy tris(pentafluorphenyl)borate,N,N-diethylanilinium tetrakis(pentafluorphenyl)borate,N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl)borate,N,N-dimethylammonium tetrakis(2,3,5,6-tetrafluorophenyl)borate,N,N-diethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,dimethyl(t-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-2,4,6-trimethylaniliniumtetrakis(2,3,4,6-tetrafluorophenyl)borate, and so forth.

The co-catalyst compound of the formula 8 may also be dialkylammonium(e.g., di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,dicyclohexylammonium tetrakis(pentafluorophenyl)borate, etc.);trialkyiphosphonium (e.g., triphenylphosphoniumtetrakis(pentafluorophenyl)borate, tri(o-tolylphosphoniumtetrakis(pentafluorophenyl)borate, tri(2,6-dimethylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate, etc.); dialkyloxonium (e.g.,diphenyloxonium tetrakis(pentafluorophenyl)borate, di(o-tolyl)oxoniumtetrakis(pentafluororphenyl)borate, di(2,6-dimethylphenyloxoniumtetrakis(pentafluorophenyl)borate, etc.); dialkylsulfonium (e.g.,diphenylsulfonium tetrakis(pentafluorophenyl)borate,di(o-tolyl)sulfonium tetrakis(pentafluorophenyl)borate,bis(2,6-dimethylphenyl)sulfonium tetrakis(pentafluorophenyl)borate,etc.); or carbonium salts (e.g., tropyliumtetrakis(pentafluorophenyl)borate, triphenylmethylcarbeniumtetrakis(pentafluorophenyl)borate, benzene(diazonium)tetrakis(pentafluorophenyl)borate, etc.).

According to the present invention, in order for the co-catalystcompound to exhibit the enhanced effect of activation, the conditionsare preferably given as follows: in the formula 6, R⁶¹ is methyl, ethyl,n-butyl, or isobutyl; in the formula 7, D is aluminum (Al), and R⁷¹ ismethyl or isobutyl; or D is boron (B), and R⁷¹ is pentafluorophenyl; andin the formula 8, [L-H]⁺ is a dimethylanilinium cation, [Z(A)₄]⁻ is[B(C₆F₅)₄]⁻, and [L]⁺ is [(C₆H₅)₃C]⁺.

The amount of the supported co-catalyst compound can be determined inconsideration of the amount of the supported transition metal compoundof the formula 1 and the required amount of the co-catalyst forsufficient activation of the transition metal compound.

As for the content of the co-catalyst compound, the molar ratio of ametal in the co-catalyst compound with respect to one mole of atransition metal in the transition metal compound of the formula 1 is1:1 to 1:100,000, preferably 1:1 to 1:10,000, more preferably 1:1 to1:5,000.

More specifically, the co-catalyst compound of the formula 6 may besupported at a molar ratio of 1:1 to 1:100,000, preferably 1:5 to1:50,000, more preferably 1:10 to 1:20,000 with respect to thetransition metal compound of the formula 1.

Further, the co-catalyst compound of the formula 7, where D is boron(B), may be used at a molar ratio of 1:1 to 1:100, preferably 1:1 to1:10, more preferably 1:1 to 1:3, with respect to the transition metalcompound of formula 1. Although dependent upon the amount of water inthe polymerization system, the co-catalyst compound of the formula 7,where D is aluminum (Al), may be used at a molar ratio of 1:1 to1:1,000, preferably 1:1 to 1:500, more preferably 1:1 to 1:100, withrespect to the transition metal compound of the formula 1.

Further, the co-catalyst of the formula 8 may be used at a molar ratioof 1:1 to 1:100, preferably 1:1 to 1:10, more preferably 1:1 to 1:4 withrespect to the transition metal compound of the formula 1.

On the other hand, the supported catalyst for olefin polymerizationaccording to the present invention may comprise a support on which thetransition metal compound of the formula 1 and the co-catalyst compoundare supported.

The support as used herein may be any kind of inorganic or organicsupport used in the preparation of a catalyst in the related art of thepresent invention.

According to one embodiment of the present invention, the support may beSiO₂, Al₂O₃, MgO, MgCl₂, CaCl₂, ZrO₂, TiO₂, B₂O₃, CaO, ZnO, BaO, ThO₂,SiO₂—Al₂O₃, SiO₂—MgO, SiO₂—TiO₂, SiO₂—V₂O₅, SiO₂—CrO_(2O) ₃,SiO₂—TiO₂—MgO, bauxite, zeolite, starch, cyclodextrine, or syntheticpolymer.

Preferably, the support includes hydroxyl groups on its surface and maybe at least one support selected from the group consisting of silica,silica-alumina, and silica-magnesia. When using a support containinghydroxyl groups on its surface, the under-mentioned transition metalcompound and the co-catalyst compound form chemical bonds to the surfaceof the support. This may result in almost no release of the catalystfrom the surface of the support during the olefin polymerization processand thus advantageously minimize particulate fouling deposits caused bycoagulation of polymer particles onto the walls of the reactor incarrying out slurry or gas polymerization to prepare a polyolefin.

The supporting method for the transition metal compound and theco-catalyst compound on a support may include: a method of directlysupporting the transition metal compound on a dehydrated support; amethod of pre-treating the support with the co-catalyst compound andthen adding the transition metal compound; a method of supporting thetransition metal compound on a support and then adding the co-catalystfor after-treatment of the support; or a method of reacting thetransition metal compound with the co-catalyst compound and then addinga support.

According to one embodiment of the present invention, the solvent asused in the supporting method is, for example, aliphatichydrocarbon-based solvents (e.g., pentane, hexane, heptane, octane,nonane, decane, undecane, dodecane, etc.); aromatic hydrocarbon-basedsolvents (e.g., benzene, monochlorobenzene, dichlorobenzene,trichlorobenzene, toluene, etc.); halogenated aliphatichydrocarbon-based solvents (e.g., dichloromethane, trichloromethane,dichloroethane, trichloroethane, etc.); or mixtures thereof.

In terms of the efficiency of the process for supporting the transitionmetal compound and the co-catalyst compound on a support, the supportingprocess may be preferably carried out at a temperature of −70 to 200°C., preferably −50 to 150° C., more preferably 0 to 100° C.

In accordance with another embodiment of the present invention, there isprovided a method for preparing a polyolefin that comprises polymerizingat least one olefin-based monomer in the presence of the afore-mentionedsupported catalyst.

In this regard, the olefin-based monomer is not specifically limited andmay include any kind of olefin monomers generally used in the relatedart of the present invention.

According to one embodiment of the present invention, the olefin-basedmonomer is at least one selected from the group consisting of C₂-C₂₀α-olefin, C₁-C₂₀ diolefin, C₃-C₂₀ cyclo-olefin, C₃-C₂₀ cyclo-diolefin,and substituted or unsubstituted styrene.

Preferably, the olefin-based monomer may be C₂-C₂₀ α-olefin, includingethylene, propylene, 1-butene, 1-pentene, or 1-hexene; C₁-C₂₀ diolefin,including 1,3-butadiene, 1,4-pentadiene, or 2-methyl-1,3-butadiene;C₃-C₂₀ cyclo-olefin or cyclodiolefin, including cyclopentene,cyclohexene, cyclopentadiene, cyclohexadiene, norbornene, ormethyl-2-norbornene; substituted styrene having a C ₁-C ₁₀ alkyl,alkoxy, halogen, amine, silyl, or haloalkyl group linked to styrene orphenyl ring of styrene; or mixtures thereof.

The polymerization step may be carried out by way of solution, gas,bulk, or suspension polymerization.

In the polymerization step conducted in the solution or slurry phase,the solvent or the olefin-based monomer itself can be used as a medium.

The solvent as used in the polymerization step may be aliphatichydrocarbon solvents (e.g., butane, isobutane, pentane, hexane, heptane,octane, nonane, decane, undecane, dodecane, cyclopentane,methylcyclopentane, cyclohexane, etc.); aromatic hydrocarbon-basedsolvents (e.g., benzene, monochlorobenzene, dichlorobenzene,trichlorobenzene, toluene, xylene, chlorobenzene, etc.); halogenatedaliphatic hydrocarbon solvents (e.g., dichloromethane, trichloromethane,chloroethane, dichloroethane, trichloroethane, 1,2-dichloroethane,etc.); or mixtures thereof.

In the polymerization step, the added amount of the supported catalystis not specifically limited and may be determined within a rangeallowing sufficient polymerization of the olefin-based monomer dependingon whether the process is carried out by way of slurry, solution, gas,or bulk polymerization.

According to the present invention, the added amount of the supportedcatalyst is 10⁻⁸ to 1 mol/L, preferably 10⁻⁷ to 10⁻¹ mol/L, morepreferably 10⁻⁷ to 10⁻² mol/L, based on the concentration of the centralmetal (M) of the transition metal compound per unit volume (L) of themonomer.

Further, the polymerization step may be carried out by way of the batchtype, semi-continuous type, or continuous type reaction.

The temperature and pressure conditions for the polymerization step arenot specifically limited and may be determined in consideration of theefficiency of the polymerization reaction depending on the types of thereaction and the reactor used.

According to the present invention, the polymerization step may becarried out at a temperature of −50 to 500° C., preferably 0 to 400° C.,more preferably 0 to 300° C. Further, the polymerization step may becarried out under the pressure of 1 to 3,000 atm, preferably 1 to 1,000atm, more preferably 1 to 500 atm.

The preparation method for polyolefin according to the present inventioncan provide a polyolefin with higher molecular weight by using theafore-mentioned supported catalyst rather than using the noveltransition metal compound in non-supported status, or the conventionaltransition metal compound in either supported or non-supported status.

In other words, the polyolefin obtained by the preparation method mayhave a weight average molecular weight (Mw) of 1,000,000 or greater,preferably 1,000,000 to 10,000,000, more preferably 1,000,000 to8,000,000, most preferably 1,000,000 to 5,000,000.

Further, the polyolefin from the preparation method may have a molecularweight distribution (Mw/Mn) of 2.0 to 4.0, preferably 2.5 to 3.5, morepreferably 2.7 to 3.0.

On the other hand, the preparation method for polyolefin according tothe present invention may further comprise, in addition to theafore-mentioned steps, a step known to those skilled in the art beforeor after the afore-mentioned steps, which are not given to limit thepreparation method of the present invention.

Hereinafter, a detailed description will be given as to the presentinvention in accordance with the preferred embodiments, which are givenby way of illustration only and not intended to limit the scope of thepresent invention.

The following synthesis procedures (i) and (ii) for the precursor andthe transition metal compound were performed in the atmosphere of inertgas, such as nitrogen or argon, according to the following Schemes 2 and3, using the standard Schlenk and glove box techniques.

The individual compounds in the Scheme 2 come in different substituents.The substituents are presented in the table given below thecorresponding compound (for example, the compound D-2 denotes a compoundhaving a hydrogen atom for R^(a) and a methyl group for R^(b) andR^(c).).

In the Scheme 2, the compound C (C-1, C-2, or C-3) was synthesized by aknown method (J. Organomet. Chem., 2005, 690, 4213).

(i) Synthesis of Precursor EXAMPLE i-1 Synthesis of Precursor D-1

A Schlenk flask containing 1,2,3,4-tetrahydroquinoline (1.00 g, 7.51mmol) and diethyl ether (16 ml) was cooled down in a cold bath at −78°C. and stirred while n-butyl lithium (3.0 mL, 7.5 mmol, 2.5 M hexanesolution) was slowly added under the nitrogen atmosphere. After one-houragitation at −78° C., the flask was gradually warmed up to the roomtemperature. A light yellowish solid precipitated, and the butane gaswas removed through a bubbler. The flask was cooled down back to −78° C.and supplied with carbon dioxide. Upon injection of carbon dioxide, theslurry-type solution turned to a clear homogenous solution. Afterone-hour agitation at −78° C., the flask was gradually warmed up −20° C.while the extra carbon dioxide was removed through the bubbler to remaina white solid as a precipitate.

Tetrahydrofuran (0.60 g, 8.3 mmol) and t-butyl lithium (4.9 mL, 8.3mmol, 1.7 M pentane solution) were sequentially added at −20° C. in thenitrogen atmosphere, and the flask was agitated for about 2 hours.Subsequently, a tetrahydrofuran solution (19 mL) containing lithiumchloride and the compound C-1 (1.06 g, 6.38 mmol) was added in thenitrogen atmosphere. The flask was agitated at −20° C. for one hour andthen gradually warmed up to the room temperature. After one-houragitation at the room temperature, water (15 mL) was added to terminatethe reaction. The solution was moved to a separatory funnel to extractthe organic phase. The extracted organic phase was put in a separatoryfunnel, and then hydrochloric acid (2 N, 40 mL) was added. After shakingup the solution for about 2 minutes, an aqueous solution of sodiumhydrocarbonate (60 mL) was slowly added to neutralize the solution. Theorganic phase was separated and removed of water with anhydrousmagnesium sulfate to eliminate the solvent and yield a sticky product.The product thus obtained was purified by the silica gel columnchromatography using a mixed solvent of hexane and ethylacetate (v/v,50:1) to yield 77.2 mg of the desired compound (43% yield).

In the ¹H NMR spectrum of the final product, there was observed a set oftwo signals at ratio of 1:1, resulting from the difficulty of rotatingabout the carbon-carbon bond (marked as a thick line in the Scheme 2)between phenylene and cyclopentadiene. In the following ¹³C NMRspectrum, the values in parenthesis are chemical shift values split dueto the difficulty of rotation.

¹H NMR(C₆D₆): δ 7.22 and 7.17 (br d, J=7.2 Hz, 1H), 6.88 (s, 2H), 6.93(d, J=7.2 Hz, 1H), 6.73 (br t, J=7.2 Hz, 1H), 3.84 and 3.80 (s, 1H, NH),3.09 and 2.98 (q, J=8.0 Hz, 1H, CHMe), 2.90-2.75 (br, 2H, CH₂),2.65-2.55 (br, 2H, CH₂), 1.87 (s, 3H, CH₃), 1.70-1.50 (m, 2H, CH₂), 1.16(d, J=8.0 Hz, 3H, CH₃) ppm.

¹³C NMR(C₆D₆): 151.64 (151.60), 147.74 (147.61), 146.68, 143.06, 132.60,132.30, 129.85, 125.02, 121.85, 121.72, 119.74, 116.87, 45.86, 42.54,28.39, 22.89, 16.32, 14.21 ppm.

EXAMPLE i-2 Synthesis of Precursor D-2

The procedures were performed in the same manner as described in Examplei-1, excepting that the compound C-2 was used rather than the compoundC-1 to synthesize the precursor compound D-2. The yield was 53%.

In the ¹H NMR spectrum of the final product, there was observed a set oftwo signals at ratio of 1:1, resulting from the difficulty of rotatingabout the carbon-carbon bond (marked as a thick line in the Scheme 2)between phenylene and cyclopentadiene.

¹H NMR(C₆D₆): δ 7.23 (d, J=7.2 Hz, 1H), 6.93 (d, J=7.2 Hz, 1H), 6.74 (brt, J=7.2 Hz, 1H), 4.00 and 3.93 (s, 1H, NH), 3.05 (br q, J=8.0 Hz, 1H,CHMe), 3.00-2.80 (br, 2H, CH₂), 2.70-2.50 (br, 2H, CH₂), 2.16 (s, 3H,CH₃), 2.04 (br s, 3H, CH₃), 1.91 (s, 3H, CH₃), 1.75-1.50 (m, 2H, CH₂),1.21 (d, J=8.0 Hz, 3H, CH₃) ppm.

¹³C NMR(C₆D₆): 151.60 (151.43), 145.56 (145.36), 143.08, 141.43, 132.90,132.68, 132.43, 129.70, 121.63, 120.01, 116.77, 46.13, 42.58, 28.42,22.97, 15.06, 14.19, 14.08, 12.70 ppm.

EXAMPLE i-3 Synthesis of Precursor D-3

The procedures were performed in the same manner as described in Examplei-1, excepting that tetrahydroquinaline was used rather than1,2,3,4-tetrahydroquinoline to synthesize the precursor compound D-3.The yield was 63%.

In the ¹H NMR spectrum of the final product, a certain signal was splitinto a set of four signals at ratio of 1:1:1:1, resulting from thedifficulty of rotating about the carbon-carbon bond (marked as a thickline in the Scheme 2) between phenylene and cyclopentadiene andisomerism pertaining to the existence of two chiral centers.

¹H NMR(C₆D₆): δ 7.33, 7.29, 7.22, and 7.17 (d, J=7.2 Hz, 1H), 6.97 (d,J=7.2 Hz, 1H), 6.88 (s, 2H), 6.80-6.70 (m, 1H), 3.93 and 3.86 (s, 1H,NH), 3.20-2.90 (m, 2H, NCHMe, CHMe), 2.90-2.50 (m, 2H, CH₂), 1.91, 1.89,and 1.86 (s, 3H, CH₃), 1.67-1.50 (m, 1H, CH₂), 1.50-1.33 (m, 1H, CH₂),1.18, 1.16, and 1.14 (s, 3H, CH₃), 0.86, 0.85, and 0.80 (d, J=8.0 Hz,3H, CH₃) ppm.

¹³C NMR(C₆D₆): 151.67, 147.68 (147.56, 147.38), 147.06 (146.83, 146.28,146.10), 143.01 (142.88), 132.99 (132.59), 132.36 (131.92), 129.69,125.26 (125.08, 124.92, 124.83), 122.03, 121.69 (121.60, 121.28), 119.74(119.68, 119.46), 117.13 (117.07, 116.79, 116.72), 47.90 (47.73), 46.04(45.85), 31.00 (30.92, 30.50), 28.00 (27.83, 27.64), 23.25 (23.00),16.38 (16.30), 14.63 (14.52, 14.18) ppm.

EXAMPLE i-4 Synthesis of Precursor D-4

The procedures were performed in the same manner as described in Examplei-1, excepting that the compound C-2 and tetrahydroquinaline were usedrather than the compound C-1 and 1,2,3,4-tetrahydroquinoline tosynthesize the precursor compound D-4. The yield was 63%.

In the ¹H NMR spectrum of the final product, a certain signal was splitinto a set of four signals at ratio of 1:1:1:1, resulting from thedifficulty of rotating about the carbon-carbon bond (marked as a thickline in the Scheme 2) between phenylene and cyclopentadiene andisomerism pertaining to the existence of two chiral centers.

1H NMR(C₆D₆): δ 7.32, 7.30, 7.22, and 7.19 (d, J=7.2 Hz, 1H), 6.97 (d,J=7.2 Hz, 1H), 6.85-6.65 (m, 1H), 4.10-3.90 (s, 1H, NH), 3.30-2.85 (m,2H, NCHMe, CHMe), 2.85-2.50 (m, 2H, CH₂), 2.15 (s, 3H, CH₃), 2.02 (s,3H, CH₃), 1.94, 1.92, and 1.91 (s, 3H, CH₃), 1.65-1.50 (m, 1H, CH₂),1.50-1.33 (m, 1H, CH₂), 1.22, 1.21, 1.20, and 1.19 (s, 3H, CH₃),1.10-0.75 (m, 3H, CH₃) ppm.

¹³C NMR(C₆D₆): 151.67 (151.57), 145.58 (145.33, 145.20), 143.10 (143.00,142.89), 141.62 (141.12), 134.08 (133.04), 132.84 (132.70, 136.60),132.50 (132.08), 129.54, 121.52 (121.16), 119.96 (119.71), 117.04(116.71), 47.90 (47.78), 46.29 (46.10), 31.05 (30.53), 28.02 (28.67),23.37 (23.07), 15.22 (15.04), 14.87 (14.02, 14.21), 12.72 (12.67) ppm.

EXAMPLE i-5 Synthesis of Precursor D-5

The procedures were performed in the same manner as described in Examplei-1, excepting that the compound C-3 and tetrahydroquinaline were usedrather than the compound C-1 and 1,2,3,4-tetrahydroquinoline tosynthesize the precursor compound D-5. The yield was 48%.

In the ¹H NMR spectrum of the final product, a certain signal was splitinto a set of four signals at ratio of 1:1:1:1, resulting from thedifficulty of rotating about the carbon-carbon bond (marked as a thickline in the Scheme 2) between phenylene and cyclopentadiene andisomerism pertaining to the existence of two chiral centers.

¹H NMR(C₆D₆): δ 7.32, 7.29, 7.22 and 7.18 (d, J=7.2 Hz, 1H), 6.96(d,J=7.2 Hz, 1H), 6.84-6.68 (m, 1H), 6.60 (d, J=7.2 Hz, 1H), 4.00-3.92(s,1H, NH), 3.30-2.90 (m, 2H, NCHMe, CHMe), 2.90-2.55 (m, 2H, CH₂), 2.27(s, 3H, CH₃), 1.94, 1.91 and 1.89 (s, 3H, CH₃), 1.65-1.54 (m, 1H, CH₂),1.54-1.38(m, 1H, CH₂), 1.23, 1.22, and 1.20 (s, 3H, CH₃), 1.00-0.75 (m,3H, CH₃) ppm.

¹³C NMR(C₆D₆): 151.51, 145.80, 145.64, 145.45, 144.40, 144.22, 143.76,143.03, 142.91, 139.78, 139.69, 139.52, 133.12, 132.74, 132.52, 132.11,129.59, 121.52, 121.19, 120.75, 120.47, 119.87, 119.69, 116.99, 116.76,47.90, 47.77, 46.43, 46.23, 32.55, 30.98, 30.51, 27.95, 27.67, 23.67,23.31, 23.06, 16.52, 15.01, 14.44, 14.05 ppm.

(ii) Synthesis of Transition Metal Compound EXAMPLE ii-1 Synthesis ofTransition Metal Compound E-1

In a dry box, the compound D-1 (0.10 g, 0.36 mmol) synthesized inExample i-1 and dimethyl ether were put into a round-bottomed flask andcooled down to −30° C. N-butyl lithium (2.5 M hexane solution, 0.2 g,0.71 mmol) was gradually added to the flask under agitation to activatethe reaction at −30° C. for 2 hours. Warmed up to the room temperature,the flask was agitated for more 3 hours for the reaction. After cooleddown back to −30° C., to the flask were added methyl lithium (1.6 Mdiethyl ether solution, 0.33 g, 0.71 mmol) and then TiCl₄.DME (DME:dimethoxyethane, 0.10 g, 0.36 mmol). The flask, while warmed up to theroom temperature, was agitated for 3 hours and then removed of thesolvent using a vacuum line. Pentane was used to extract the compound.The removal of the solvent produced 0.085 g of the final compound as abrownish powder (60% yield).

¹H NMR (C₆D₆): δ 7.09 (d, J=7.2 Hz, 1H), 6.91 (d, J=7.2 Hz, 1H), 6.81(t, J=7.2 Hz, 1H), 6.74 (s, 2H), 4.55 (dt, J=14, 5.2 Hz, 1H, NCH₂), 4.38(dt, J=14, 5.2 Hz, 1H, NCH₂), 2.50-2.30 (m, 2H, CH₂), 2.20 (s, 3H), 1.68(s, 3H), 1.68 (quintet, J=5.2 Hz, CH₂), 0.72 (s, 3H, TiMe), 0.38 (s, 3H,TiMe) ppm.

¹³C{¹H} NMR (C₆D₆): 161.46, 142.43, 140.10, 133.03, 130.41, 129.78,127.57, 127.34, 121.37, 120.54, 120.51, 120.34, 112.52, 58.50, 53.73,49.11, 27.59, 23.27, 13.19, 13.14 ppm.

EXAMPLE ii-2 Synthesis of Transition Metal Compound E-2

The procedures were performed in the same manner as described in Exampleii-1, excepting that the compound D-2 was used rather than the compoundD-1 to synthesize the transition metal compound E-2. The yield was 53%.

¹H NMR (C₆D₆): δ 7.10 (d, J=7.2 Hz, 1H), 6.91 (d, J=7.2 Hz, 1H), 6.81(t, J=7.2 Hz, 1H), 4.58 (dt, J=14, 5.2 Hz, 1H, NCH₂), 4.42 (dt, J=14,5.2 Hz, 1H, NCH₂), 2.50-2.38 (m, 2H, CH₂), 2.32 (s, 3H), 2.11 (s, 3H),2.00 (s, 3H), 1.71 (s, 3H), 1.67 (quintet, J=5.2 Hz, CH₂), 0.72 (s, 3H,TiMe), 0.38 (s, 3H, TiMe) ppm.

¹³C{¹H} NMR (C₆D₆): 161.58, 141.36, 138.41, 137.20, 132.96, 129.70,127.53, 127.39, 126.87, 121.48, 120.37, 120.30, 113.23, 56.50, 53.13,49.03, 27.64, 23.34, 14.21, 13.40, 12.99, 12.94 ppm. Anal. Calc.(C₂₂H₂₇NSTi): C, 68.56; H, 7.06; N, 3.63. Found: C, 68.35 H, 7.37 N,3.34%.

EXAMPLE ii-3 Synthesis of Transition Metal Compound E-3

The procedures were performed in the same manner as described in Exampleii-1, excepting that the compound D-3 was used rather than the compoundD-1 to synthesize the transition metal compound E-3. The yield was 51%.The final product was identified as a 1:1 mixture (the direction of thethiophene cyclic radical to the direction of the methyl radical ontetrahydroquinoline).

¹H NMR (C₆D₆): δ 7.11 and 7.08 (d, J=7.2 Hz, 1H), 6.96 and 6.95 (d,J=7.2 Hz, 1H), 6.82 and 6.81 (t, J=7.2 Hz, 1H), 6.77 and 6.76 (d, J=7.2Hz, 1H), 6.74 and 6.73 (d, J=7.2 Hz, 1H), 5.42 (m, 1H, NCH), 2.75-2.60(m, 1H, CH₂), 2.45-2.25 (m, 1H, CH₂), 2.24 and 2.18 (s, 3H), 1.73 and1.63 (s, 3H), 1.85-1.50 (m, 2H, CH₂), 1.17 and 1.15 (d, J=4.8 Hz, 3H),0.76 and 0.70 (s, 3H, TiMe), 0.42 and 0.32 (s, 3H, TiMe) ppm.

¹³C{¹H} NMR (C₆D₆): 159.58, 159.28, 141.88, 141.00, 139.63, 138.98,134.45, 130.85, 130.50, 129.59, 129.50, 129.47, 127.23, 127.20, 127.17,127.11, 120.77, 120.70, 120.40, 120.00, 119.96, 119.91, 118.76, 118.57,113.90, 110.48, 59.61, 56.42, 55.75, 51.96, 50.11, 49.98, 27.41, 27.11,21.89, 20.09, 19.67, 12.94, 12.91, 12.65 ppm.

EXAMPLE ii-4 Synthesis of Transition Metal Compound E-4

The procedures were performed in the same manner as described in Exampleii-1, excepting that the compound D-4 was used rather than the compoundD-1 to synthesize the transition metal compound E-4. The yield was 57%.The final product was identified as a 1:1 mixture (the direction of thethiophene cyclic radical to the direction of the methyl radical ontetrahydroquinoline).

¹H NMR (C₆D₆): δ 7.12 and 7.10 (d, J=7.2 Hz, 1H), 6.96 and 6.94 (d,J=7.2 Hz, 1H), 6.82 and 6.81 (t, J=7.2 Hz, 1H), 5.45 (m, 1H, NCH),2.75-2.60 (m, 1H, CH₂), 2.45-2.20 (m, 1H, CH₂), 2.34 and 2.30 (s, 3H),2.10 (s, 3H), 1.97 (s, 3H), 1.75 and 1.66 (s, 3H), 1.85-1.50 (m, 2H,CH₂), 1.20 (d, J=6.8 Hz, 3H), 0.76 and 0.72 (s, 3H, TiMe), 0.44 and 0.35(s, 3H, TiMe) ppm.

¹³C{¹H} NMR (C₆D₆): 160.13, 159.86, 141.33, 140.46, 138.39, 137.67,136.74, 134.83, 131.48, 129.90, 129.78, 127.69, 127.65, 127.60, 127.45,126.87, 126.81, 121.34, 121.23, 120.21, 120.15, 119.15, 118.93, 114.77,111.60, 57.54, 55.55, 55.23, 51.73, 50.43, 50.36, 27.83, 27.67, 22.37,22.31, 20.53, 20.26, 14.29, 13.51, 13.42, 13.06, 12.80 ppm.

EXAMPLE ii-5 Synthesis of Transition Metal Compound E-5

The procedures were performed in the same manner as described in Exampleii-1, excepting that the compound D-5 was used rather than the compoundD-1 to synthesize the transition metal compound E-5. The yield was 57%.The final product was identified as a 1:1 mixture (the direction of thethiophene cyclic radical to the direction of the methyl radical ontetrahydroquinoline).

¹H NMR (C₆D₆): δ 7.12 and 7.09 (d, J=7.2 Hz, 1H), 6.96 and 6.94 (d,J=7.2 Hz, 1H), 6.82 and 6.80 (t, J=7.2 Hz, 1H), 6.47 and 6.46 (d, J=7.2Hz, 1H), 6.45 and 6.44 (d, J=7.2 Hz, 1H), 5.44 (m, 1H, NCH), 2.76-2.60(m, 1H, CH₂), 2.44-2.18 (m, 1H, CH₂), 2.28 and 2.22 (s, 3H), 2.09 (s,3H), 1.74 and 1.65 (s, 3H), 1.88-1.48 (m, 2H, CH₂), 1.20 and 1.18 (d,J=7.2 Hz, 3H), 0.77 and 0.71(s, 3H, TiMe), 0.49 and 0.40 (s, 3H, TiMe)ppm.

¹³C{¹H} NMR (C₆D₆): 159.83, 159.52, 145.93, 144.90, 140.78, 139.93,139.21, 138.86, 135.26, 131.56, 129.69, 129.57, 127.50, 127.46, 127.38,127.24, 121.29, 121.16, 120.05, 119.96, 118.90, 118.74, 117.99, 117.74,113.87, 110.38, 57.91, 55.31, 54.87, 51.68, 50.27, 50.12, 34.77, 27.58,27.27, 23.10, 22.05, 20.31, 19.90, 16.66, 14.70, 13.11, 12.98, 12.68ppm.

EXAMPLE ii-6 Synthesis of Transition Metal Compound E-6

The transition metal compound E-6 was synthesized according to thefollowing Scheme 3.

Methyl lithium (1.63 g, 3.55 mmol, 1.6 M diethyl ether solution) wasadded dropwise to a diethyl ether solution (10 mL) containing thecompound D-4 (0.58 g, 1.79 mmol). The solution was agitated overnight atthe room temperature and cooled down to −30° C. Then, Ti(NMe₂)₂Cl₂ (0.37g, 1.79 mmol) was added at once. After 3-hour agitation, the solutionwas removed of all the solvent with a vacuum pump. The solid thusobtained was dissolved in toluene (8 mL), and Me₂SiCl₂ (1.16 g, 8.96mmol) was added to the solution. The solution was agitated at 80° C. for3 days and removed of the solvent with a vacuum pump to obtain a reddishsolid compound (0.59 g, 75% yield). The ¹H NMR spectrum showed theexistence of two stereo-structural compounds at ratio of 2:1.

¹H NMR (C₆D₆): δ 7.10 (t, J=4.4 Hz, 1H), 6.90 (d, J=4.4 Hz, 2H), 5.27and 5.22 (m, 1H, NCH), 2.54-2.38 (m, 1H, CH₂), 2.20-2.08 (m, 1H, CH₂),2.36 and 2.35 (s, 3H), 2.05 and 2.03 (s, 3H), 1.94 and 1.93 (s, 3H),1.89 and 1.84 (s, 3H), 1.72-1.58 (m, 2H, CH₂), 1.36-1.28 (m, 2H, CH₂),1.17 and 1.14 (d, J=6.4, 3H, CH₃) ppm.

¹³C{¹H} NMR (C₆D₆): 162.78, 147.91, 142.45, 142.03, 136.91, 131.12,130.70, 130.10, 128.90, 127.17, 123.39, 121.33, 119.87, 54.18, 26.48,21.74, 17.28, 14.46, 14.28, 13.80, 13.27 ppm.

(iii) Preparation of Supported Catalyst

EXAMPLE iii-1

In a glove box, the transition metal compound E-4 of Example ii-4 (0.03g, 75 vitriol) was put into a Schlenk flask. After the flask was takenout of the glove box, about 5.1 ml of methylaluminoxane (a solutioncontaining 10 wt. % of methylaluminoxane in toluene, 7.5 mmol of Al,supplied by Albemarle) was slowly added at 10° C. The flask was agitatedat 10° C. for 10 minutes and at 25° C. for 60 more minutes.

Apart from that, silica (XPO-2412, 0.5 g, supplied by Grace) was putinto another Schlenk flask (100 ml) in the glove box, and a solutioncontaining the transition metal compound and the methylaluminoxane wasslowly added to the flask. Subsequently, the flask was agitated at 0° C.for about one hour, at 65° C. for about one more hour, and then at 25°C. for about 24 more hours.

The resultant solution thus obtained was dried out under vacuum to yield0.85 g of a free flowing supported catalyst.

EXAMPLE iii-2

The procedures were performed in the same manner as described in Exampleiii-1, excepting that the transition metal compound E-5 (0.029 g, 75μmol) of Example ii-5 was used, to yield a supported catalyst.

COMPARATIVE EXAMPLE iii-1

The procedures were performed in the same manner as described in Exampleiii-1, excepting that bisindenylzirconium dichloride (0.029 g, 75 μmol)was used rather than the transition metal compound E-4, to yield asupported catalyst.

(iv) Preparation of Polyolefin

The individual polymerization reaction was carried out in an airtightautoclave using required amounts of a dehydrated solvent forpolymerization, a transition metal compound, a co-catalyst compound, andmonomers for copolymerization.

After completion of the polymerization, the polymer product was measuredin regard to the molecular weight and the molecular weight distributionby the GPC (Gel Permeation Chromatography) (instrument: PL-GPC220supplied by Agilent), and the melting point by the DSC (DifferentialScanning calorimetry) (instrument: Q200 supplied by TA Instruments). Themeasured properties of the individual polymers are presented in thefollowing Table 1.

EXAMPLE iv-1

0.1 g of the supported catalyst of Example iii-1 and 20 ml of n-hexanewere put into a flask, and ethylene was added at a rate of 0.05 g/minfor 10 minutes to the flask under agitation to inducepre-polymerization.

Apart from that, an autoclave (capacity: 2 L, stainless steel) waspurged with nitrogen and filled with 1 L of n-hexane as a solvent forpolymerization. Then, 2 mmol of triisobutyl aluminum (supplied byAldrich) and the pre-polymerized supported catalyst were added insequence. The autoclave was warmed up to 70° C., supplied with ethylenegas, and maintained at ethylene partial pressure of 7 bar to allow apolymerization reaction for one hour.

After completion of the polymerization reaction, the resultant solutionwas cooled down to the room temperature and removed of the extraethylene gas. Subsequently, the polyethylene powder dispersed in thesolvent was filtered out and dried out in a vacuum oven at 80° C. for atleast 15 hours to yield a polyethylene (141 g).

EXAMPLE iv-2

The procedures were performed in the same manner as described in Exampleiv-1, excepting that the supported catalyst was used withoutpre-polymerization, to yield a polyethylene (130 g).

EXAMPLE iv-3

The procedures were performed in the same manner as described in Exampleiv-1, excepting that the supported catalyst of Example iii-2 was used,to yield a polyethylene (112 g).

COMPARATIVE EXAMPLE iv-1

The procedures were performed in the same manner as described in Exampleiv-1, excepting that the supported catalyst of Comparative Example iii-1was used, to yield a polyethylene (101 g).

COMPARATIVE EXAMPLE iv-2 Non-Supported Catalyst

An autoclave (capacity: 2 L, stainless steel) was purged with nitrogenand filled with 1 L of n-hexane as a solvent for polymerization. Then,10 ml of methylaluminoxane (a solution containing 10 wt. % ofmethylaluminoxane in toluene, 7.5 mmol of Al, supplied by Albemarle) wasadded.

Subsequently, a solution of the transition metal compound E-4 of Exampleii-4 (0.031 g, 75 μmol) in toluene was added to the autoclave, which wasthen warmed up to 70° C.

When the temperature of the autoclave reached 70° C., ethylene (partialpressure: 7 bar) was added to allow polymerization for 30 minutes.

After completion of the polymerization reaction, the resultant solutionwas cooled down to the room temperature and removed of the extraethylene gas. Subsequently, the polyethylene powder dispersed in thesolvent was filtered out and dried out in a vacuum oven at 80° C. for atleast 15 hours to yield a polyethylene (110 g).

COMPARATIVE EXAMPLE iv-3 Non-Supported Catalyst

An autoclave (capacity: 2 L, stainless steel) was purged with nitrogenand filled with 1 L of n-hexane as a solvent for polymerization. Then,10 ml of methylaluminoxane (a solution containing 10 wt. % ofmethylaluminoxane in toluene, 7.5 mmol of Al, supplied by Albemarle) wasadded.

Subsequently, a solution of bisindenylzirconium dichloride (0.029 g, 75μmol) in toluene was added to the autoclave, which was then warmed up to70° C.

When the temperature of the autoclave reached 70° C., ethylene (partialpressure: 7 bar) was added to allow polymerization for 30 minutes.

After completion of the polymerization reaction, the resultant solutionwas cooled down to the room temperature and removed of the extraethylene gas. Subsequently, the polyethylene powder dispersed in thesolvent was filtered out and dried out in a vacuum oven at 80° C. for atleast 15 hours to yield a polyethylene (95 g).

TABLE 1 Molecular Molecular weight Catalytic weight distributionCatalyst activity (Mw) (Mw/Mn) Example iv-1 Example iii-1 1.4 2,822,0002.85 (Compound E-4) Example iv-2 Example iii-1 1.3 3,207,000 2.96(Compound E-4) Example iv-3 Example iii-2 1.1 1,013,000 2.91 (CompoundE-5) Comparative Comparative 1.0 290,000 2.50 Example iv-1 Example iii-1([Ind]₂ZrCl₂) Comparative Non-supported 29.3 883,000 2.18 Example iv-2(Compound E-4) Comparative Non-supported 25.3 284,000 2.84 Example iv-3([Ind]₂ZrCl₂) (Note: The unit of catalytic activity is (a) (weight (kg)of PE)/weight (g) of catalyst) per unit time for supported catalysts(e.g., Examples iv-1, iv-2, and iv-3, and Comparative Example iv-1), or(b) (weight (kg) of PE)/(moles (mmol) of Metal) per unit time fornon-supported catalysts (e.g., Comparative Examples iv-2 and iv-3).)

As can be seen from Table 1, the supported catalysts in which thetransition metal compound of the present invention were fixed on asupport as in Examples iv-1, iv-2, and iv-3 were capable of providing apolymer with a considerable high molecular weight, relative to thenon-supported catalysts of Comparative Example iv-2.

In contrast, the use of a different transition metal compound as inComparative Examples iv-1 and iv-3 resulted in production of a polymerhaving a low molecular weight irrespective of whether the transitionmetal compound was supported or not.

Further, as can be seen from Examples iv-1 and iv-2, the supportedcatalysts of the present invention were capable of providing a polymerwith high molecular weight irrespective of whether a pre-polymerizationwas conducted prior to the olefin polymerization reaction.

1. A supported catalyst comprising a transition metal compoundrepresented by the following formula 1 and a co-catalyst compound,wherein the transition metal compound and the co-catalyst compound arebound to a support:

wherein M is a Group 4 transition metal; Q¹ and Q² are independently ahalogen, C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₆-C₂₀ aryl,C₁-C₂₀ alkyl C₆-C₂₀ aryl, C₆-C₂₀ aryl C₁-C₂₀ alkyl, C₁-C₂₀ alkylamido,C₆-C₂₀ arylamido, or C₁-C₂₀ alkylidene; R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸,R⁹, and R¹⁰ are independently hydrogen; C₁-C₂₀ alkyl with or without anacetal, ketal, or ether group; C₂-C₂₀ alkenyl with or without an acetal,ketal, or ether group; C₁-C₂₀ alkyl C₆-C₂₀ aryl with or without anacetal, ketal, or ether group; C₆-C₂₀ aryl C₁-C₂₀ alkyl with or withoutan acetal, ketal, or ether group; or C₁-C₂₀ silyl with or without anacetal, ketal, or ether group, wherein R¹ and R² can be linked to eachother to form a ring; R³ and R⁴ can be linked to each other to form aring; and at least two of R⁵ to R¹⁰ can be linked to each other to forma ring; and R¹¹, R¹², and R¹³ are independently hydrogen; C₁-C₂₀ alkylwith or without an acetal, ketal, or ether group; C₂-C₂₀ alkenyl with orwithout an acetal, ketal, or ether group; C₁-C₂₀ alkyl C₆-C₂₀ aryl withor without an acetal, ketal, or ether group; C₆-C₂₀ aryl C₁-C₂₀ alkylwith or without an acetal, ketal, or ether group; C₁-C₂₀ silyl with orwithout an acetal, ketal, or ether group; C₁-C₂₀ alkoxy; or C₆-C₂₀aryloxy, wherein R¹¹ and R¹², or R¹² and R¹³ can be linked to each otherto form a ring.
 2. The supported catalyst for olefin polymerization asclaimed in claim 1, wherein M is titanium (Ti), zirconium (Zr), orhafnium (Hf); Q¹ and Q² are independently methyl or chlorine; R¹, R²,R³, R⁴, and R⁵ are independently hydrogen or methyl; and R⁶, R⁷, R⁸, R⁹,R¹⁰, R¹¹, R¹², and R¹³ are independently hydrogen.
 3. The supportedcatalyst for olefin polymerization as claimed in claim 2, wherein atleast one of R³ and R⁴ is methyl; and R⁵ is methyl.
 4. The supportedcatalyst for olefin polymerization as claimed in claim 1, wherein theco-catalyst compound is at least one selected from the group consistingof compounds represented by the following formula 6, 7, or 8:—[Al(R⁶¹)—O]_(a)—  [Formula 6] wherein R⁶¹ is independently a halogenradical, a C₁-C₂₀ hydrocarbyl radical, or a halogen-substituted C₁-C₂₀hydrocarbyl radical; and a is an integer of 2 or above,D(R⁷¹)₃   [Formula 7] wherein D is aluminum (Al) or boron (B); and R⁷¹is independently a halogen radical, a C₁-C₂₀ hydrocarbyl radical, or ahalogen-substituted C₁-C₂₀ hydrocarbyl radical,[L-H]⁺[Z(A)₄]⁻ or [L]⁺[Z(A)₄]⁻  [Formula 8] wherein L is a neutral orcationic Lewis acid; Z is a Group 13 element; and A is independently aC₆-C₂₀ aryl or C₁-C₂₀ alkyl radical having at least one hydrogen atomsubstituted with a halogen radical, a C₁-C₂₀ hydrocarbyl radical, aC₁-C₂₀ alkoxy radical, or a C₆-C₂₀ aryloxy radical.
 5. The supportedcatalyst for olefin polymerization as claimed in claim 4, wherein in theformula 6, R⁶¹ is methyl, ethyl, n-butyl, or isobutyl; in the formula 7,D is aluminum, and R⁷¹ is methyl or isobutyl; or D is boron, and R⁷¹ ispentafluorophenyl; and in the formula 8, [L-H]⁺ is a dimethylaniliniumcation, [Z(A)₄]⁻ is [B(C₆F₅)₄]⁻, and [L]⁺ is [(C₆H₅)₃C]⁺.
 6. Thesupported catalyst for olefin polymerization as claimed in claim 1,wherein the content of the co-catalyst compound is given such that amolar ratio of a metal in the co-catalyst compound with respect to onemole of a transition metal in the transition metal compound of theformula 1 is 1:1 to 1:10,000.
 7. The supported catalyst for olefinpolymerization as claimed in claim 1, wherein the support is SiO₂,Al₂O₃, MgO, MgCl₂, CaCl₂, ZrO₂, TiO₂, B₂O₃, CaO, ZnO, BaO, ThO₂,SiO₂—Al₂O₃, SiO₂—MgO, SiO₂—TiO₂, SiO₂—V₂O₅, SiO₂—CrO₂O₃, SiO₂—TiO₂—MgO,bauxite, zeolite, starch, or cyclodextrine.
 8. A method for preparing apolyolefin, comprising polymerizing at least one olefin-based monomer inthe presence of the supported catalyst as claimed in claim
 1. 9. Themethod as claimed in claim 8, wherein the olefin-based monomer is atleast one selected from the group consisting of C₂-C₂₀ α-olefin, C₁-C₂₀diolefin, C₃-C₂₀ cyclo-olefin, and C₃-C₂₀ cyclo-diolefin.
 10. The methodas claimed in claim 8, wherein the polyolefin has a weight averagemolecular weight (Mw) of 1,000,000 to 10,000,000.